CN101914079B - Method for producing vitamin C - Google Patents
Method for producing vitamin C Download PDFInfo
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- CN101914079B CN101914079B CN201010264225XA CN201010264225A CN101914079B CN 101914079 B CN101914079 B CN 101914079B CN 201010264225X A CN201010264225X A CN 201010264225XA CN 201010264225 A CN201010264225 A CN 201010264225A CN 101914079 B CN101914079 B CN 101914079B
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Abstract
The invention relates to a method for producing vitamin C. The method comprises the following steps of: performing esterification reaction between a crystal of sodium 2-keto-L-gulonic and n-butyl alcohol under the catalysis of concentrated sulfuric acid to obtain the solution of n-butyl 2-keto-L-gulonic; adding Na2CO3 into the solution to perform lactonization reaction to obtain sodium vitamin C; and finally performing acidification and active carbon decolourization on the sodium vitamin C to obtain the vitamin C. The method of the invention can greatly reduce production cost, reduce water used for the production, solve the problems of environment pollution and potential safety hazard, shorten production period and achieve the product yield of over 90 percent.
Description
Technical field
The invention belongs to biochemical industry products production technical field, be specifically related to ascorbic working method.
Background technology
Vitamins C (Vc) is one of 26 kinds of definite jointly essential drugses of the World Health Organization and the United Nations Industrial Development Organization; Be that needed by human and self can not synthetic nutritions; Its disease-prevention health function and assisting therapy effect are played more and more important effect to health of people; Therefore, ascorbic industrial scale constantly enlarges, and method and technology is being updated.
The Lai Shi method is the chemical synthesis process that is used for industrial production Vc the earliest.The seventies in 20th century, the Chinese research personnel adopt two-step fermenting that the compound method of Vc is improved on the basis of Lai Shi method.No matter the still two-step fermenting of China's initiative of Lai Shi method all needs to make ancient dragon sour (2-KLG) through microbial fermentation.2-KLG is an important midbody during Vc produces, and its after chemical reaction process just can be converted into Vc.According to selected different reagent wherein, two-step fermenting can be divided into sour conversion method and alkali conversion method.Because the former used concentrated hydrochloric acid is more serious to equipment corrosion, and is prone to cause environmental pollution, therefore replaced by the latter gradually.The 2-KLG transformation efficiency of alkali conversion method is high, and easy and simple to handle, and is lighter to corrosion on Equipment, so be suitable for the large-scale production of Vc.
Traditional method is to make ancient imperial acid solution with sodium colombate (2KGA-Na) solution through cationic exchange, the ancient imperial acid crystal of preparation behind condensing crystal, oven dry back chemosynthesis Vc.In this step, the regeneration of Zeo-karb will consume a large amount of alkali acid solutions and tap water, and the discharging of waste liquid also causes serious pollution to environment.Simultaneously, crystallisation process needs cooling, consume significant amount of energy.And the ancient imperial acid crystal that is used for esterification also needs can use behind the vacuum drying, also can bring the significant amount of energy loss.On the other hand, in traditional Vc compound method, need use a large amount of anhydrous methanols, because the character of its highly volatile often causes its a large amount of losses in production and preservation process.Generally speaking the Vc compound method cycle is long at present, and facility investment is many, and cost is high, and yield is low.
Summary of the invention
The purpose of this invention is to provide a kind of ascorbic working method, it comprises the steps: the sodium colombate crystal under sulphuric acid catalysis, carries out esterification with propyl carbinol and produces the positive butyl acetate solution of ancient dragon acid; Add Na again
2CO
3, carrying out lactonization reaction and generate vitamin C sodium salt, last sodium ascorbate carries out acidifying and activated carbon decolorizing obtains vitamins C.
The condition of described esterification is:
Ingredient proportion: sodium colombate crystal: the vitriol oil: propyl carbinol=1kg: 0.267～0.309kg: 2.78～3.09kg;
Temperature of reaction: 70 ℃～82 ℃;
Reaction vacuum tightness :-0.068MPa～-0.075MPa;
Reaction times: 3～6h
After reaction finishes, reaction soln is filtered collection, and with hot propyl carbinol washing leaching cake, washings is collected in the lump.
The massfraction of sodium colombate is 80%～90% in the said sodium colombate crystal, and water cut is 5%～15%.
The reaction conditions of said lactonization reaction is following:
Positive butyl acetate solution concentration: 20%～28% (g/ml) of ancient dragon acid;
Lactonization reaction Na
2CO
3Consumption: 1.03～1.06 times of theoretical amount;
Content of water in system: 1.5%～2.5% (W/W) before the lactonization reaction;
Lactonization reaction vacuum tightness :-0.065MPa～-0.080MPa;
Lactonization reaction temperature: 75 ℃～80 ℃;
The lactonization reaction time: 4～6h;
After reaction finished, reacting liquor while hot was filtered, and abandons filtrating, stays filter cake, and filter cake washs with propyl carbinol.
Wherein theoretical amount is amount of substance/2 * 106 of 2KGA-Na when feeding intake.
Said Na
2CO
3Consumption confirm by following principle:
Na
2CO
3Quality=(remaining H
2SO
4Amount of substance/2 * 106 of amount of substance * 106+ 2KGA-Na when feeding intake) * 1.03～1.06.
Content of water in system is lower than at 1.5% o'clock before the lactonization reaction, drops into Na in the reaction system through water is added to
2CO
3, make that water cut is increased to 1.5～2.5% in the system; When reacting precursor is a water cut when being higher than 2.5%,, make that water cut is reduced to 1.5～2.5% in the system through before feeding intake, dewatering with propyl carbinol steam carrier distillation method.
The water that generates in said esterification and the lactonization reaction is removed with propyl carbinol steam carrier distillation method.
With the raw product of the sodium ascorbate that obtains behind the lactonization reaction, drop in the methanol solution, carry out acidifying, activated carbon decolorizing, filtration according to prior art, obtain vitamin c solution.
Can reach more than 90% according to the yield of the thick Vc of method of the present invention (equal conversion rate of esterification * lactonize the yield of transformation efficiency * acidization), and the yield of prior art two-step fermentation can improve 10 percentage points at least for being about 80%.And method of the present invention can reduce production costs water during minimizing is produced, solution environmental pollution and security hidden trouble, shortening production cycle, raising product yield greatly.This shows that technology of the present invention will promote the technical progress of Vc method greatly, have the favorable industrial development prospect.
Embodiment
Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.Under the situation that does not deviate from the present invention's spirit and essence, modification or replacement to the inventive method, step or condition are done all belong to scope of the present invention.
If do not specialize the conventional means that used technique means is well known to those skilled in the art among the embodiment.
Embodiment 1
Take by weighing 2KGA-Na (purity is about 90% for content 89.28%, water cut 0.62%) after the 112g oven dry in there-necked flask; And adding 500ml anhydrous methanol (water cut≤0.1%); Add the 32g vitriol oil after opening stirring and evenly mixing, slowly heat up (heating in water bath is set 80 ℃), mixeding liquid temperature is final constant about 67 ℃; The reaction beginning; Dewater with the methanol steam carrier distillation method, through fed-batch mode isopyknic anhydrous methanol (water cut≤0.1%) is added in the system simultaneously, react and finish experiment behind about 5h.Calculating ancient imperial sour esterification yield result is 89.5%;
Embodiment 2
Take by weighing 2KGA-Na (purity is about 90% for content 89.28%, water cut 0.62%) after the 112g oven dry in three flasks; And adding 500ml propyl carbinol (water cut 0.37%); Add the 32g vitriol oil again after opening stirring and evenly mixing, slowly heat up (heating in water bath is set 80 ℃) is when solution temperature reaction beginning during approximately to 75 ℃; Use propyl carbinol steam carrier distillation method dewater (vacuum tightness for-0.070MPa); Propyl carbinol under the condensation can continue Returning reacting system and recycle, and reaction is to finish experiment behind the 3h total time, measure in the water-and-oil separator water layer volume be about 6ml.It is 92.62% that experiment finishes the ancient imperial sour esterification yield of back calculating.
Embodiment 3
Take by weighing the 2KGA-Na that 132g do not dry (content is 84.81%, water cut 9.7%, purity is about 94%) in there-necked flask; And adding 500ml propyl carbinol (water cut 0.37%); Add the 38.64g vitriol oil again after opening stirring and evenly mixing, slowly heat up (heating in water bath is set 80 ℃) is when solution temperature reaction beginning during approximately to 75 ℃; Use the propyl carbinol steam carrier distillation method (vacuum tightness-0.072MPa) that dewaters after half a hour; Propyl carbinol under the condensation can continue Returning reacting system and recycle, and reaction is to finish experiment behind the 4h total time, measure in the water-and-oil separator water layer volume be about 9ml.It is 95.96% that experiment finishes the ancient imperial sour esterification yield of back calculating.
Embodiment 4
Take by weighing 387g 2KGA-Na (content is 83.24%, water cut 9.56%) and drop in the 2L there-necked flask, open stirring and evenly mixing behind the adding 1500ml propyl carbinol; Add the 66ml vitriol oil (density 1.84, content >=98%) again, slowly heat up (heating in water bath is set 80 ℃); When solution temperature time reaction beginning approximately to 75 ℃; (vacuum tightness-0.070MPa), reaction total time is 4h, and esterification is water outlet 44.5ml altogether to use propyl carbinol steam carrier distillation method to dewater after half a hour.Reaction back solution filtered while hot, filter cake is with the propyl carbinol washing of about 200ml heat, and washings is incorporated in the filtrating, obtains pale brown look esterifying liquid 1788ml altogether, and recording its moisture content is 2.1% (massfraction).
Embodiment 5
Esterification liquid is transferred in the 2L there-necked flask, and heating in water bath to 75 ℃ takes by weighing the required 135g soda ash light powder of Theoretical Calculation.The powdered sodium carbonate that stirs half amount approximately of dropping into earlier down uses propyl carbinol steam carrier distillation method dewater (vacuum tightness 0.076MPa) behind the stirring reaction 20min in esterifying liquid.Dropping into residue powdered sodium carbonate 1/2 behind the 40min measures in esterifying liquid; Use the propyl carbinol steam carrier distillation method (vacuum tightness-0.078MPa) that dewaters behind the stirring reaction 10min; To remain powdered sodium carbonate behind the 30min and devote entirely in the esterifying liquid, use the propyl carbinol steam carrier distillation method (vacuum tightness-0.078MPa) that dewaters.Stopped reaction after total reaction time reaches 6h.
Embodiment 6
Lactonization reaction mixed solution filtered while hot, filter cake is with fitting the washing of calorimetric butanol solution.Gained yellow solid matter quality 461.7g, VcNa content is 58.41%.Calculating at last from sodium colombate to the VcNa yield is 91.27%.The waste liquid that lactonizes is 1500ml altogether, its middle ancient times dragon acid content 0.095g/L, VcNa content 0.117g/L.From sodium colombate to the VcNa total conversion rate is 91.32%.
Embodiment 7
Take by weighing 132g VcNa pressed powder (content 58%) and be dissolved in 170ml water, using massfraction is that 50% sulphuric acid soln is regulated and promptly obtained Vc solution between above-mentioned pH value of solution to 2.1～2.3, consumes the sulphuric acid soln about about 38ml altogether.Vc solution stirring 30min after-filtration, filtrating changes over to leaves standstill the 40min layering in the 500mL separating funnel, tell upper strata brown solution (the about 28ml of volume); Lower floor's solution is heated to 45 ℃, stirs to add the acid gac of 1.36g, leaves standstill 2h behind the insulation 40min; Filter and remove gac also with an amount of methanol wash filter cake, washings is incorporated filtrating into and is obtained solution 250ml altogether, and stream adds 625ml methyl alcohol in solution; The gained mixed solution leaves standstill 4h under 25 ℃, centrifugal removal solid precipitation obtains the 912ml that filtrates; Vc content and purity are respectively 0.0702g/ml and 90%, the filtrating condensing crystal, centrifugally promptly get thick Vc.
Claims (6)
1. ascorbic working method, it comprises the steps:
Under sulphuric acid catalysis, sodium colombate crystal and propyl carbinol are carried out esterification, generate the positive butyl acetate solution of ancient dragon acid;
In the positive butyl acetate solution of ancient dragon acid, add Na
2CO
3Carry out lactonization reaction, generate sodium ascorbate;
Sodium ascorbate is carried out acidifying and activated carbon decolorizing, obtains vitamins C,
Wherein, the condition of described esterification is:
Ingredient proportion: sodium colombate crystal: the vitriol oil: propyl carbinol=1kg: 0.267～0.309kg: 2.78～3.09kg;
Temperature of reaction: 70 ℃～82 ℃;
Reaction vacuum tightness :-0.068MPa～-0.075MPa;
Reaction times: 3～6h;
After reaction finishes, reaction soln is filtered collection, and use the propyl carbinol washing leaching cake, washings is collected in the lump,
The reaction conditions of said lactonization reaction is following:
Positive butyl acetate solution concentration: 20%～28% (g/ml) of ancient dragon acid;
Lactonization reaction Na
2CO
3Consumption: 1.03～1.06 times of theoretical amount;
Content of water in system: 1.5%～2.5% (W/W) before the lactonization reaction;
Lactonization reaction vacuum tightness :-0.065MPa～-0.080MPa;
Lactonization reaction temperature: 75 ℃～80 ℃;
The lactonization reaction time: 4～6h;
After reaction finished, reacting liquor while hot was filtered, and abandons filtrating, stays filter cake, and filter cake washs with propyl carbinol.
2. working method according to claim 1 is characterized in that, the massfraction of sodium colombate is 80%～90% in the said sodium colombate crystal, and water cut is 5%～15%.
3. working method according to claim 1 is characterized in that, said Na
2CO
3Consumption confirm by following principle:
Na
2CO
3Quality=(remaining H
2SO
4Amount of substance/2 * 106 of amount of substance * 106+ 2KGA-Na when feeding intake) * 1.03～1.06.
4. working method according to claim 1 is characterized in that said content of water in system is lower than at 1.5% o'clock, with water and the Na that drops in the reaction system
2CO
3Mixing makes content of water in system reach 1.5～2.5%.
5. working method according to claim 1 is characterized in that said content of water in system is higher than at 2.5% o'clock, before feeding intake, removes with propyl carbinol steam carrier distillation method, makes content of water in system reach 1.5～2.5%.
6. working method according to claim 1 is characterized in that, the water that generates in said esterification and the lactonization reaction is removed with propyl carbinol steam carrier distillation method.
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|---|---|---|---|
| CN201010264225XA CN101914079B (en) | 2010-08-20 | 2010-08-20 | Method for producing vitamin C |
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|---|---|---|---|
| CN201010264225XA CN101914079B (en) | 2010-08-20 | 2010-08-20 | Method for producing vitamin C |
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| CN110372647A (en) * | 2019-08-08 | 2019-10-25 | 安徽丰原发酵技术工程研究有限公司 | It is a kind of to prepare ascorbic method by a step acid system of raw material of Cologne hydrochlorate |
| CN110437188A (en) * | 2019-08-08 | 2019-11-12 | 安徽丰原发酵技术工程研究有限公司 | It is a kind of to prepare ascorbic method by the nitrogenous base conversion method of raw material of Cologne hydrochlorate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391770A (en) * | 1989-06-12 | 1995-02-21 | Rhone Poulenc Rorer S.A. | Process for preparing ascorbic acid |
| CN1122802A (en) * | 1994-12-28 | 1996-05-22 | 华东理工大学 | Method for preparing ascorbic acid by quantitative conversion of sodium colombate |
| CN101284824A (en) * | 2008-06-06 | 2008-10-15 | 郑州拓洋实业有限公司 | Preparation method of cenolate |
-
2010
- 2010-08-20 CN CN201010264225XA patent/CN101914079B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391770A (en) * | 1989-06-12 | 1995-02-21 | Rhone Poulenc Rorer S.A. | Process for preparing ascorbic acid |
| CN1122802A (en) * | 1994-12-28 | 1996-05-22 | 华东理工大学 | Method for preparing ascorbic acid by quantitative conversion of sodium colombate |
| CN101284824A (en) * | 2008-06-06 | 2008-10-15 | 郑州拓洋实业有限公司 | Preparation method of cenolate |
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